Dyestuff preparations



Patented Mar. 2, 1943 2,312,328 DYESTUFF PREPARATIONS Friedrich Felix, Basel, Switzerland, assignor to the firm of Society of Chemical Industry in Basle, Basel, Switzerland N Drawing. Application May 24, 1940, Serial No. 337,081. In Switzerland June 8, 1939 3 Claims.

It has been found that acetate rayon may be dyed in shades of blue of surprising tinctorialstrength if, for the dyeing process, those dyestuif preparations be used which consist of mixtures of two or more blue dyestuffs, and correspond to the general formula in which :0 represents cyanogen, halogen or an SOz-alkyl group, 3/ represents halogen or a nitro group, R1 is an aromatic nucleus of the benzene series in which the N=N-group and the CH -CH OH group stand in the para position to one another, and R2 stands for hydrogen or an alkyl group.

[ These mixtures of dyestufis possess a better power of exhaustion when compared with that of the individual components of the mixtures. But those dyestuffs which have, as individuals, a relatively good power of exhaustion may have this property improved quite considerably by incorporating them into mixtures in the manner explained above. The manufacture of the preparations can take place either in the manufacture of the dyestuffs, by making use of a mixture of intermediates, the choice of which is governed by consideration of the general formula mentioned above, or the finished dyestuffs may be dissolved in a common solvent, from which the mixture of dyestufls is precipitated in a fine state of subdivision, or the finished dyestuffs may be ground together into a finely subdivided state, or the dyestuffs, which are already in a finely dispersed state, may be added to the same dyebath.

Dyestuffs which find application by the present process are described, for example, in U. S. A. Patents Nos. 2,173,417; 2,053,817;2,053,818; 2,082,- 156 and 2,155,755. They are prepared according to the usual methods, by use of diazo compounds derived from l-amino- 2-cyano-6-chloro-4-nitrobenzene, 1 amino 2:4-dinitrobenzene-6-methyl sulfone, l-amino-fi-chloro-Z:4-dinitrobenzene, 1- amino 6 cyano 2:4 dinitrobenzene, etc., and coupling components, such as N-ethylhydro yethylamino-3methyl-benzene, N dihydroxyethylamino-B-methylbenzene, N hydroxyethylamino-3-methylbenzene, N dihydroxyethylamino-B- methyl-G-methoxybenzene, N hydroxyethylamino-S-methyl-B-methoxybenzene, as well as N-dihydroxyethylamino 3 acetylamino-fi-methoxybenzene, etc.

Among these preparations, those are of particular value which contain at least two dyestuffs dyeing blue shades 'and possessing the general formula I CHr-CHPOH wherein :1: stands for a member of the group consisting of cyanogen, halogen and SOz-alkyl, 3/ stands for a member of the group consisting of halogen and N02, provided that only one of the two symbols y and :1: stands for halogen, R1 stands for an aromatic nucleus of the benzene series in which N=N-group and the CHrCHr-OH group stand in para position to one another and in which a substituent of the group consisting of alkyl, O-alkyl and NH-acyl stands in ortho position to the --N=N-group, and R2 stands for a member of the group consisting of hydrogen and alkyl. These preparations dye acetate rayon in shades which are of much greater tinctorial strength than those obtained with either of the individual components alone. They may contain 2, 3 or still more single components. Those dyestuffs are particularly valuable in which the radical R2 stands for methyl, ethyl or hydroxyethyl, and in the manufacture of which compounds suchas 1-amino-2-chloro-4-nitro 6 cyanobenzene or 1 amino-2-methyl-sulfone-4z6 dinitrobenzene are used as diazo components. Dyev stuffs of this nature have been described in U. S. A. Patent Nos. 2,173,417; 2,053,817; 2,053,- 818; and 2,082,156. These mixtures form the most valuable blue dyestuffs for acetate rayon which have been produced to date.

Example 1 Equal parts of the dyestuif obtained by the union of diazotized 1-amino-2:4-dinitrobenzene- 6-methy1 sulfone with N-dihydroxyethylamino- 3-methylbenzene and of the dyestuff obtained by the union of the .same diazo compound with N- hydroxyethylamino-3-methyl-6-methoxybenzene are ground with about 10 parts of sulfite cellulose waste liquor or of another dispersing agent of similar action. The paste thus obtained may be used for the dyeing of acetate rayon. Pastes of this nature can also be converted into preparations of similar behaviour in powder form by careful drying and subsequent grinding.

The blue dyeings obtained with these preparations are considerably more intensive thanthe dyeings of similar shade which are obtained by use of the individual components.

Example 2 a soap solution of 6 per cent strength, or preferably with about an equal quantity of a solution of 6 per cent strength of a soap-like substance, and the suspension is diluted with water to 300 parts. 10 parts of acetate rayon are entered into this bath, the temperature is raised during hour to 75-80 C. and the rayon is worked at this temperature for about hour further, after which it is rinsed and dried. The acetate rayon is dyed a deep blue shade.

The following dyestuffs may be mentioned as being examples selected from the group of bluedyeing dyestuffs which can give valuable dyeings when used in mixtures:

be mixed only in the mixtures given in the above table.

What I claim is:

1. Dyestuil preparations containing at least two dyestuffs dyeing blue shades of the general formula CHrCHr-OH -group'stand in para position to one another and in which a substituent of the group consisting Diazo component Coupling component Shade (a) l-amino-zzi-dinitrobenune-dmetbylsulione lgl-dihydroxyethylemino-3-methyl-6-methoxybenzene an me (la) 1-amino-2:i-dinitmbenzene-t-methyl sulfone N-hydroxyethylamino-B-methyl-fi-methoxybenune {(41) 1-amino-2:i-dlnitrobenzene-6-methyl sullone N-ethoxyethylamino-il-methyl-(S-methoxybemene Do an (b) l-amino-2:4-dinitrobenzene-6-methyl sulfone N-methylhydroxyethylamino-tmethyl-fi-methoxybenzene (a) 1-amino-2z4-dlnitrobenzene-6-methyl sulfons {(b) 1-amino-2z4-dinitrobenzene-6-methyl sulione (a) l-amino-2zi-dinitro enzene-6-methyi sulfono {(b) l-amino-2z4-dinitrobenzene-6-methyl sulfone (a) 1-amino-2z4-dinitmbenzene-6-methyl sulfone {(b) l-amino-2z4-dinitrobenzene-6-methyl sull'one (a) 1-ainino-2:4-dinltrobenzene-6-methy1sulione {(b) l-aminu-izkdinitrobenzene-G-methyl sulfone (a) l-amino-Zkdinitro-B-chlorobenmne {(0) l-amino-2z4-dinitro-ehlorobenzene (a) l-amino-Zzi-dinitro-G-chlorobenrene Lb) l-amino-Zzi-dlnitrobemene-G -methyl sulione (a) l-amlno-ZM-dlnitro-Erchlorobenzene {(b) 1-amino-2:4-dinltrobenmne-6-methylsu1ione (a) i-amino-Z-cyano-G-chloroA-nltrobenzene {(b) i-amino-zcyano-fi-chloroi-nitrobenzcne (a) i-amino-z-cyano-ii-chlownitrobenzene {(0) l-amino-z-cyano-fi-chlorwnitrobenzene (a) l-amino-2:4dinitrobwene-6-methylsu1lonc 1(2)) i-amino-m-dinitrobenrene-e-methylsuliona (c) 1-amino-2z4-diflltr0bei1I-ene6-meth5'lsulfone (a) l-amino-2z4-dinitrobenzene-fi-metliylsifllono (b) l-amino-zzi-dinitrobenzene-fi-methylsulfone (c) l-amind2:'idinitrobenzeue-6-methy1sulfone (d) l-amino-2zi-dinltrobenzene-6-methylsulfone (a) 1-amino-m-dlnitrobenzeneemethylsulione {(b) l-aminaZzi-dinitrobenmedmethylsulione (c) i-amlno-za-dinltrobenzenefi-ethylsulfme N-dihydroxyethylsmino-a-msthyl-G-methoxybenzene an 8 l N-hydroxyethylamino-3-methyl-6-methoxybenzene N -ethoxyethylamino-a-methyl-e-methoxybenzene a iN-dlhydroxyethylaminod-methyl-ii-methoxybenmfle N-hydroxyethylamino-ii-methyl-fi-methoxybenzene i N-ethoxyethylamlno-3-methyl-6-methoxybenzene N-methylhydroxyethyl-amino-3-Inethyl-6-methoxybenzeno N-dlhy,droxyetln lan1ino-3-xnethyl-ii-methoxylxanzene mg N-hydroryethylamino-.B-methyl-(i-methoxybenunc N-etho xyethylamino-a methyl-o-methorybenzene It is naturally also possible to mix the individual dyestuffs within the confines of the said of alkyl, O-alkyl and NI-I-acyl stands in ortho position to the --N=N-group, and R2 stands group as desired, that is to S y. y need n 75 foramember of the group consisting of CH3, Cal-Is 2,312,398 and CHzCHzOH, which dyestufl preparations wherein R1 stands for" an aromatic nucleus of the benzene series in which the -N=N-group and the \CHPCHPQH -gr:up stand in para position to one another and in which a. suostituent of the group consisting of aikyl, 'D-all'lijl and NH-acyl stands in ortho position to the --l ?=N-group. and stands or a member of. the group oonslsting of CH2, C1315 d CH:-Eie---QH, which dyestufi preparations Late 1 an in shades of s more increased 2? than the individual components,

3. Dyestufi preparations containing at least two dyestufls dyeing blue shades of the general formula,

wherein R1 stands for an aromatic nucleus of the benzene series in which the --N=N-group and the /R:

CHr-CEr-GH more taeressed tinetoriel power then the indi-= vidual eemponents.

FRIEDRICH ELIE. 

